CN1138800C - Method for preparing graft copolymer of methylmethacrylate-butadiene-styrene having superior anti-stress whitening properties - Google Patents
Method for preparing graft copolymer of methylmethacrylate-butadiene-styrene having superior anti-stress whitening properties Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
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Abstract
The present invention relates to a method of preparing an impact-reinforcement agent for polyvinylchloride (PVC) resin having superior anti-stress whitening properties, and specifically to a method for preparing a graft copolymer of methylmethacrylate-butadiene-styrene (MBS) comprising 3 steps of graft-copolymerizing monomers such as alkylmethacrylate, acrylate, and an ethylene-unsaturated aromatic compound to a rubber latex, in sequence.
Description
Background of invention
(a) invention field
The present invention relates to have the impact modifying agent of excellent anti stress whitening properties polyvinyl chloride (PVC).More particularly, the present invention relates to the preparation method of methyl methacrylate-butadiene-styrene graft copolymer (MBS), when it is applied in the poly (vinyl chloride) resin composition, have height equilibrated shock strength, transparency, anti-stress whitening and processing characteristics.
(b) explanation of correlation technique
Polyvinyl chloride (PVC) is a kind of polymkeric substance that comprises greater than 50% vinylchlorid, becomes fragile when therefore being hit.In order to improve this defective of polyvinyl chloride resin, studied the whole bag of tricks so far.For example, will be such as vinylbenzene, methyl methacrylate or acrylonitrile monemer are grafted on the bivinyl rubber latex, improving shock resistance, yet, under this situation, when it is molded as sheet material, there is the shortcoming that reduces the product transparency and produce stress whitening.
We know that the performance matter of methyl methacrylate-butadiene-styrene (MBS) resin is formed each monomeric content of graft copolymer to a great extent, polymerization process reaches as the content of the rubber latex of base material and the influence of particle diameter.In order to improve shock strength, usual method is content and the particle diameter that increases rubber latex, yet transparency reduces owing to be dispersed in that the scattering degree of the big particle diameter of graft polymerization composition granule in the polyvinyl chloride resin increases.And, when the refractive index difference of the refractive index of polyvinyl chloride resin and graftomer is very big, perhaps, when producing deformation,, can cause that stress whitening increases owing to a little less than the bounding force between MBS resin and the polyvinyl chloride resin, form microvoid easily.
In order to obtain having the excellent shock resistance and the graft copolymer particles of anti-stress whitening properties, content and particle diameter, graft polymerization procedure and composition about rubber grain, many researchs have been carried out, and know, particularly when the purposes of rubber latex was restricted, transparency of products and shock strength significantly were listed as by the influence of grafted monomer content and polymerization process.
The example that improves the method for anti-stress whitening properties and shock strength in the prior art comprises: swelling capacity by the control rubber polymer and refractive index people such as (USP 4431772) Katto; Use multistep polymerization method people such as (USP 4352910) Katto; And the various monomer segmentation grafted methods of control people such as (USP 4857592) Hoshino.All these methods are all used linking agent usually in graft polymerization reaction.Yet all these are attempted, and the performance of polyvinyl chloride resin that contains grafted particles is all because the formation thrust is restricted as dispersive flake not, and this is considered to be caused by the processing parameter that operational condition etc. is correlated with.
Summary of the invention
Consider the problems referred to above, the method that the purpose of this invention is to provide methyl methacrylate-butadiene-styrene graft copolymer that a kind of preparation has excellent impact resistance, transparency, anti-stress whitening properties and workability, carry out polymerization with three step graft polymerization methods, wherein monomer is such as alkyl methacrylate, and the unsaturated aromatic substance of acrylate and vinyl is grafted on the rubber latex successively.
For achieving the above object, the method that a kind of preparation has the methyl methacrylate-butadiene-styrene graft copolymer of excellent anti-stress whitening properties has been proposed, this method comprises the steps:
A) preparation fs polymkeric substance: the rubber latex and the 5-25 part weight methacrylic acid alkyl ester that adds of 70-80 part weight are carried out graft polymerization;
B) preparation subordinate phase polymkeric substance: the fs polymkeric substance and the 0.0001-5 part weight acrylamide acid esters that adds of step a) preparation are carried out graft polymerization; And
C) preparation phase III polymkeric substance: subordinate phase polymkeric substance and the unsaturated aromatic substance of 5-30 part weight vinyl that adds and the graft crosslinking agent of no more than 5 parts of weight of step b) preparation are carried out graft polymerization.
Description of Preferred Embodiments
The following describes the preferred embodiments of the invention.The rubber latex that the present invention uses is a styrene butadiene rubbers, and it can use divinyl or isoprene as main component, with other vinyl monomer of 1-3 part, with traditional emulsion polymerisation process preparation.Be for meeting the needs of control multipolymer refractive index with vinyl monomer as raw material in the copolyreaction, or will give the crosslinking copolymers structure.The content and the type that are used for the vinyl monomer of copolyreaction can change according to the required character of product, can use at least 35% monomer of final copolymer.
Styrene-butadiene copolymer rubber comprises preferably:
(i) 65-85 part weight butadiene;
(ii) 5-35 part weight vinyl monomer; With optional
(iii) at least 5 parts of weight is as the monomer of graft crosslinking agent.
The example that is used for the vinyl monomer of styrene butadiene rubbers is vinylbenzene, vinyl cyanide, Vinylstyrene, based on the alkyl acrylate of ethyl propenoate and butyl acrylate, wherein can use one or more monomers, and two or more monomers is used in combination more favourable.
The graft crosslinking agent can be selected from following monomeric at least a: Vinylstyrene, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), the dimethacrylate triglycol ester, dimethacrylate 1,3 butanediol ester, aryl methacrylate and diacrylate 1,3 butanediol ester.The consumption of graft crosslinking agent is not more than 5 parts, preferably uses 0.1-2.0 part, is used to improve transparency and anti-stress whitening properties.
Graft polymerization reaction can be undertaken by series of steps:
A) preparation fs polymkeric substance: the rubber latex and the 5-25 part weight methacrylic acid alkyl ester that adds of 70-80 part weight are carried out graft polymerization;
B) preparation subordinate phase polymkeric substance: the fs polymkeric substance and the 0.0001-5 part weight acrylamide acid esters that adds of step a) preparation are carried out graft polymerization;
C) preparation phase III polymkeric substance: subordinate phase polymkeric substance and the unsaturated aromatic substance of 5-30 part weight vinyl that adds and the graft crosslinking agent of no more than 5 parts of weight of step b) preparation are carried out graft polymerization.
Thus, can prevent that transparency, shock resistance and anti-stress whitening properties from becoming bad.
The optional graft crosslinking agent of using helps to improve the adaptability of impact modifying agent to PVC base resin by increasing by the content of grafted monomer in the step c), and its consumption is not more than 5 parts, preferably is not more than 2 parts.
The present invention will be described in more detail with reference to following embodiment and comparative example.Yet these embodiment obviously only are used to the present invention is described rather than limit the scope of the invention.The term that uses among the following embodiment " part " and " % " are meant " weight part " and " weight % ", unless otherwise indicated.
Embodiment
In the embodiments of the invention, will mix, and stir simultaneously and heat with the graft copolymer of method for preparing and the oxidation inhibitor and the acid that join wherein, from polymkeric substance, separate water outlet then, filtering product is also dry, obtains the MBS powder, and itself and PVC base mixed with resin are used for analyzing.
PVC base resin concentrates be comprise 100 parts of polyvinyl chloride (PVC) RESINS (polymerization degree: 800), 1.5 parts of tinbase thermo-stabilizers, 1.0 parts of internal lubricants, 0.5 lubricant especially, a kind of product of 0.5 part of processing aid and 0.3 part of tinting material is before the use,, cool off then in 130 ℃ of thorough mixing with high speed agitator.
For assessing PVC of the present invention base resin, per 100 parts of PVC base resin adds 7 parts of impact modifying agents, with it by roll and carry out hot pressing in 190 ℃ and make the thick sheet of 3mm.The sheet of making thus is cut into test film accurately, is used for carrying out beam type (Izod) impact test and transparence test, and determines transparence and turbidity with turbidometer according to the ASTM standard.
Anti-stress whitening character is measured by such method with Falling Dart instrument (Falling Dart machine), promptly change weight be 9 kilograms and diameter be 20 millimeters test specimen in 3 meter per seconds, measure transparency change.Calculate anti-stress whitening value according to following equation, this value is low more, and anti-stress whitening properties is good more.
Anti-stress whitening degree=[(transparency after the transparency-variation before changing)/(transparency before changing)] * 100
Embodiment 1
[preparation methyl methacrylate-butadiene-styrene graft copolymer]
(preparation of rubber latex)
150 parts of deionized waters, with as 0.5 part of buffered soln of additive, 0.8 part of potassium oleate, 0.0047 part of ethylenediaminetetraacetic acid four sodium, 0.003 part of ferrous sulfate, 0.02 part of formolation sodium hydrosulfite and 0.11 part of diisopropylbenzyl hydrogen peroxide, the time join in 120 liters of pressure polymerisation reaction vessels that agitator is housed in beginning.
The first step, in said mixture, add 20 parts of divinyl, 20 parts of vinylbenzene and 0.2 part of Vinylstyrene, carry out polyreaction in 35 ℃, when polymerisation conversion surpasses added monomeric 90% the time, add 52 parts of divinyl, 7.5 parts of vinylbenzene, 0.3 part of Vinylstyrene and 0.3 part of potassium oleate, as second step, polyreaction 10 hours, obtain the styrene butadiene rubbers latex of particle diameter 1020 thus, final polymerisation conversion is 98%.
(the first step polyreaction)
The rubber latex that 70 parts (solid content) obtains above joins in the reactor with a blind end, inflated with nitrogen then, and add 11.5 parts of methyl methacrylates, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, and polyreaction is 1 hour then.
(the second step polyreaction)
2.5 part ethyl acetate, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the polymkeric substance that the first step polyreaction obtains, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
16 parts of vinylbenzene, with 0.2 part of potassium oleate as additive, 0.01 part formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
Above-mentioned polymerization results obtains 100 parts of products, adds the latex monomer of same amount.
Embodiment 2 and 3, comparative example 1 and 2
(preparation among the embodiment 2)
Use the identical method of embodiment 1, with 75 parts of rubber latexs, 9 parts of methyl methacrylates, 2.5 parts of ethyl propenoates and 13.5 parts of vinylbenzene.
(preparation among the embodiment 3)
Use the identical method of embodiment 1, with 80 parts of rubber latexs, 6.5 parts of methyl methacrylates, 2.5 parts of ethyl propenoates and 11 parts of vinylbenzene.
(preparation in the comparative example 1)
Use the identical method of embodiment 1, with 87 parts of rubber latexs, 3 parts of methyl methacrylates, 2.5 parts of ethyl propenoates and 7.5 parts of vinylbenzene.
(preparation in the comparative example 2)
Use the identical method of embodiment 1, with 63 parts of rubber latexs, 15.2 parts of methyl methacrylates, 2.5 parts of ethyl propenoates and 19.3 parts of vinylbenzene.
Measure the foregoing description 2 and 3, the Izod shock strength of the product that comparative example 1 and 2 obtains (23 ℃), transparency, mist degree and anti-stress whitening properties the results are shown in table 1, have wherein used rubber latex and various monomeric different compositions.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Izod shock strength (23 ℃) | 76 | 87 | 90 | 95 | 35 |
| Transparency | 65.5 | 65.3 | 65.0 | 64.2 | 66 |
| Mist degree | 7.0 | 8.2 | 10.3 | 23.0 | 5.2 |
| Anti-stress whitening | 6.3 | 8.5 | 11 | 20.2 | 4.0 |
Table 1 as seen, obviously, embodiment 1,2 and 3 product has excellent shock resistance, transparency, mist degree and anti-stress whitening, the suitable composition that wherein has the methyl methacrylate-butadiene-styrene graft copolymer of excellent anti stress whitening is to comprise 70-80 part rubber latex, 5-25 part alkyl methacrylate, 0-5 part acrylate and 5-30 divide vinyl unsaturated aromatic substance.
Comparative example 3 and 4
[preparation in the comparative example 3]
(the first step polyreaction)
2.5 part ethyl propenoate and as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide joins in 75 parts of (solid content) rubber latexs in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the second step polyreaction)
13.5 part vinylbenzene, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the polymkeric substance that the first step polyreaction obtains, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
9 parts of methyl methacrylates, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
[preparation in the comparative example 4]
(the first step polyreaction)
13.5 part vinylbenzene and as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide joins in 75 parts of (solid content) rubber latexs in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the second step polyreaction)
9 parts of methyl methacrylates, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, add in the polymkeric substance that the first step polyreaction of falling in lines obtains, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
2.5 part ethyl propenoate, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
Measure Izod shock strength (23 ℃), transparency, mist degree and the anti-stress whitening properties of the comparative example 3 and 4 products of above-mentioned change graft polymerization order, compare, the results are shown in table 2 with embodiment 2.
Table 2
| Izod shock strength (23 ℃) | Transparency | Mist degree | Anti-stress whitening | |
| Embodiment 2 | 87 | 65.3 | 8.2 | 8.5 |
| Comparative example 3 | 73 | 64.2 | 13.2 | 15 |
| Comparative example 4 | 67 | 65.3 | 15.7 | 14.7 |
As shown in table 2, obviously, Izod shock strength, transparency, mist degree and the anti-stress whitening that has changed the comparative example 3 of graft polymerization order and 4 product is poorer than embodiment's 2.
Embodiment 4, comparative example 5 and 6
[preparation among the embodiment 4]
(the first step polyreaction)
11 parts of methyl methacrylates, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in 73 parts of (solid content) rubber latexs in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the second step polyreaction)
1.5 part butyl acrylate, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the polymkeric substance that the first step polyreaction obtains, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
14.5 part vinylbenzene, with as 0.2 part of potassium oleate of additive, 0.01 part of formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
[preparation in the comparative example 5]
(the first step polyreaction)
11 parts of methyl methacrylates and as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, successive joins in 73 parts of (solid content) rubber latexs in 45 minutes, and polyreaction is 2 hours then.
(the second step polyreaction)
Comprise 1.5 parts of butyl acrylates and 14.5 fens vinylbenzene, with 0.2 part of potassium oleate as additive, 0.01 the mix monomer of part formolation sodium hydrosulfite and 0.08 part of tertbutyl peroxide joined in 45 minutes in the polymkeric substance that the first step polyreaction obtains, polyreaction is 2 hours then.
[preparation in the comparative example 6]
(the first step polyreaction)
Comprise 11 parts of methyl methacrylates and 1.5 fens butyl acrylates, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, successive joins in 73 parts of (solid content) rubber latexs in 45 minutes, and polyreaction is 2 hours then.
(the second step polyreaction)
14.5 branch vinylbenzene and as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, successive joins in the polymkeric substance that the first step polyreaction obtains in 45 minutes, and polyreaction is 2 hours then.
Measure Izod shock strength, transparency, mist degree and the anti-stress whitening properties of the product of the embodiment 4 of above-mentioned step preparation according to graft polymerization segmentation and comparative example 5 and 6, the results are shown in table 3.
Table 3
| Embodiment 4 | Comparative example 5 | Comparative example 6 | |
| Izod shock strength (23 ℃) | 80 | 87 | 76 |
| Transparency | 65.7 | 65.1 | 64.8 |
| Mist degree | 8.0 | 9.7 | 9.7 |
| Anti-stress whitening | 8.0 | 14.5 | 16.2 |
As shown in table 3, obviously, Izod shock strength, transparency and the anti-stress whitening of the product of the embodiment 4 that obtains by three step polymerizations are better than the performance of the product of the comparative example 5 that obtains with two-stage polymerization and 6.
Embodiment 5 and comparative example 7
[preparation among the embodiment 5]
(the first step polyreaction)
9 parts of methyl methacrylates, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, join in 75 parts of (solid content) rubber latexs in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the second step polyreaction)
2.5 part ethyl propenoate, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, add in the polymkeric substance that the first step polyreaction of falling in lines obtains, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
13 parts of vinylbenzene, 0.5 a part Vinylstyrene is done the graft crosslinking agent, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture is added in the rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
[preparation in the comparative example 7]
(the first step polyreaction)
9 parts of methyl methacrylates, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, join in 75 parts of (solid content) rubber latexs in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the second step polyreaction)
2.5 part ethyl propenoate, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, join in the polymkeric substance that the first step polyreaction obtains, and this mixture added in the row rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 1 hour then.
(the 3rd step polyreaction)
11 parts of vinylbenzene, 2.5 a part Vinylstyrene is done the graft crosslinking agent, with as 0.35 part of potassium oleate of additive, 0.015 part of formolation sodium hydrosulfite and 0.118 part of tertbutyl peroxide, join in the second step polymkeric substance that obtain of polyreaction, and this mixture added in the row rubber latex in 70 ℃ of successive in 30 minutes, polyreaction is 2 hours then.
Measure Izod shock strength (23 ℃), transparency, mist degree and the anti-stress whitening properties of the product of the embodiment 5 of the above-mentioned consumption that has changed the graft crosslinking agent and comparative example 7, and compare, the results are shown in table 4 with embodiment 2.
Table 4
| Izod shock strength (23 ℃) | Transparency | Mist degree | Anti-stress whitening | |
| Embodiment 2 | 87 | 65.3 | 8.2 | 8.5 |
| Embodiment 5 | 80 | 66.2 | 7.5 | 6.7 |
| Comparative example 7 | 69 | 66.5 | 6.5 | 5.2 |
As shown in table 4, by comparing embodiment 2,5 and the result of comparative example 7 gained, as can be known when as the amount of the Vinylstyrene of linking agent in about 01.-2.0 part scope the time, the transparency of polyvinyl chloride (PVC) RESINS improves, but when the amount of Vinylstyrene surpasses 2.0 parts, the shock strength variation of polychloroethylene composition.
As mentioned above, reference example and comparative example are given polyvinyl chloride (PVC) RESINS according to the methyl methacrylate-butadiene-styrene graft copolymer of the present invention's preparation and are had excellent shock resistance, transparency, anti-stress whitening and workability.
Claims (6)
1. method for preparing methyl methacrylate-butadiene-styrene graft copolymer with excellent anti-stress whitening properties, the method comprising the steps of:
A) preparation fs polymkeric substance: the rubber latex and the 5-25 part weight methacrylic acid alkyl ester that adds of 70-80 part weight are carried out graft polymerization, based on the methyl methacrylate-butadiene-styrene graft copolymer of 100 weight parts;
B) preparation subordinate phase polymkeric substance: the fs polymkeric substance and the 0.0001-5 part weight acrylamide acid esters that adds of step a) preparation are carried out graft polymerization, based on the methyl methacrylate-butadiene-styrene graft copolymer of 100 weight parts; With
C) preparation phase III polymkeric substance: the subordinate phase polymkeric substance and the unsaturated aromatic substance of 5-30 part weight vinyl that adds of step b) preparation are carried out graft polymerization, based on the methyl methacrylate-butadiene-styrene graft copolymer of 100 weight parts.
2. according to the process of claim 1 wherein that rubber latex comprises:
(i) 65-85 part weight butadiene is based on the rubber latex of 100 weight parts; With
(ii) 5-35 part weight vinyl monomer is based on the rubber latex of 100 weight parts.
3. according to the process of claim 1 wherein that rubber latex further comprises the graft crosslinking agent of no more than 5 parts of weight, based on the rubber latex of 100 weight parts.
4. according to the method for claim 3, wherein the graft crosslinking agent is at least a Vinylstyrene, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), dimethacrylate triglycol ester, the dimethacrylate 1 of being selected from, 3 butanediol esters, aryl methacrylate and diacrylate 1,3 butanediol ester.
5. according to the method for claim 2, therein ethylene base monomer is at least a ethyl propenoate and the butyl acrylate that is selected from vinylbenzene, vinyl cyanide, Vinylstyrene, acrylic acid alkyl ester group.
6. according to the process of claim 1 wherein that the graft polymerization step c) carries out polymerization under the condition that further adds the agent of no more than 2.0 parts of weight graft crosslinkings, based on the methyl methacrylate-butadiene-styrene graft copolymer of 100 weight parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2000-0063410A KR100454023B1 (en) | 2000-10-27 | 2000-10-27 | Process for preparation of graft copolymer of methylmethacrylate -butadiene-styrene havng superior anti-stress whitening property |
| KR2000/63410 | 2000-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1394215A CN1394215A (en) | 2003-01-29 |
| CN1138800C true CN1138800C (en) | 2004-02-18 |
Family
ID=19695735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018033342A Expired - Lifetime CN1138800C (en) | 2000-10-27 | 2001-10-26 | Method for preparing graft copolymer of methylmethacrylate-butadiene-styrene having superior anti-stress whitening properties |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6855786B2 (en) |
| KR (1) | KR100454023B1 (en) |
| CN (1) | CN1138800C (en) |
| WO (1) | WO2002034806A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199743A (en) * | 2005-01-18 | 2006-08-03 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition and molded article |
| CN102492238B (en) * | 2011-11-30 | 2013-07-10 | 山东瑞丰高分子材料股份有限公司 | Modifying agent resin for PVC (polyvinyl chloride)-M high-impact pipe as well as preparation and use methods thereof |
| CN105254789B (en) * | 2015-10-20 | 2019-02-05 | 佳易容相容剂江苏有限公司 | A kind of copolymerzation with cross-linking resin and preparation method thereof |
| CN106280077A (en) * | 2016-08-05 | 2017-01-04 | 安徽蓝通科技股份有限公司 | A kind of PVC of crack resistence and preparation method thereof |
| CN117551242B (en) * | 2024-01-09 | 2024-03-19 | 山东东临新材料股份有限公司 | Preparation method of impact modifier ACM resin |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581683B2 (en) | 1978-04-07 | 1983-01-12 | ジェイエスアール株式会社 | Manufacturing method of impact resistant resin |
| JPS592704B2 (en) | 1980-10-23 | 1984-01-20 | 呉羽化学工業株式会社 | Vinyl chloride resin composition |
| JPS57212246A (en) | 1981-06-23 | 1982-12-27 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPS63199255A (en) | 1987-02-13 | 1988-08-17 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| US5268430A (en) * | 1991-09-16 | 1993-12-07 | General Electric Company | Methacrylate-butadiene-styrene graft polymer and its PVC blends having low yellowness, good clarity, and improved impact strength |
| FR2721151B1 (en) * | 1994-06-08 | 1996-08-14 | Labavia | Improvements to transmissions of vehicles equipped with eddy current retarders, and to fasteners for such transmissions. |
| KR0164627B1 (en) * | 1994-06-30 | 1999-03-20 | 사공수영 | Preparation of methylmethacrylate-butadiene-styrene resin |
| JPH093142A (en) * | 1995-06-15 | 1997-01-07 | Japan Synthetic Rubber Co Ltd | Rubber-reinforced vinyl polymer and thermoplastic polymer composition |
| JPH09296015A (en) | 1996-04-30 | 1997-11-18 | Kao Corp | Manufacture of abs polymer latex |
| DE69923267T2 (en) * | 1998-09-09 | 2006-03-30 | Rohm And Haas Co. | Improved MBS impact modifier |
-
2000
- 2000-10-27 KR KR10-2000-0063410A patent/KR100454023B1/en active IP Right Grant
-
2001
- 2001-10-26 US US10/168,721 patent/US6855786B2/en not_active Expired - Lifetime
- 2001-10-26 WO PCT/KR2001/001822 patent/WO2002034806A1/en active Application Filing
- 2001-10-26 CN CNB018033342A patent/CN1138800C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1394215A (en) | 2003-01-29 |
| US6855786B2 (en) | 2005-02-15 |
| KR100454023B1 (en) | 2004-10-20 |
| KR20020032771A (en) | 2002-05-04 |
| WO2002034806A1 (en) | 2002-05-02 |
| US20030027916A1 (en) | 2003-02-06 |
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